Herbicidal pyridine sulfonamide

ABSTRACT

A pyridine sulfonylurea herbicide, composition thereof and a method for its use that results in the control of blackgrass in cereal crops and general control of all plant growth.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent applicationSer. No. 07/666,109, filed Mar. 7, 1991, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a certain herbicidal sulfonamide orsulfonylurea compound, an agriculturally suitable composition thereofand a method for its use as a general or selective preemergent orpostemergent herbicide.

New compounds effective for controlling the growth of undesiredvegetation are in constant demand. In the most common situation, suchcompounds are sought to selectively control the growth of weeds inuseful crops such as cotton, rice, corn, wheat and soybeans, to name afew. Unchecked weed growth in such crops can cause significant losses,reducing profit to the farmer and increasing costs to the consumer. Inother situations, herbicides are desired which will control all plantgrowth. Examples of areas in which complete control of all vegetation isdesired are areas around railroad tracks, storage tanks and industrialstorage areas. There are many products commercially available for thesepurposes, but the search continues for products which are moreeffective, less costly and environmentally safe.

The "sulfonylurea" herbicides are an extremely potent class ofherbicices discovered within the last few years which generally consistof a sulfonylurea bridge, --SO₂ NHCONH--, linking two aromatic orheteroaromatic rings.

WO 88/04297 discloses herbicidal pyridinesulfonylureas of the formula##STR1## wherein

J is, among others, ##STR2##

R₁ is R_(f) or R_(g) ;

R_(g) is, among others, C₁ -C₃ haloalkyl; and

R₂ is, among others, CO₂ R₉.

Although the compound of the invention is within the above genericscope, it is not disclosed therein.

EP-A-327,251 discloses pyridinesulfonylureas of the formula ##STR3##wherein

R is C₁ -C₃ alkyl; and

R₁ is C₁ -C₂ fluoralkyl and their use for controlling blackgrass.

EP-A-232,067 discloses 3-carboxamide pyridinesulfonylureas. However,this reference does not disclose the instant compound or the blackgrassutility therein.

EP-A-237,292 discloses 3-carboxamide pyridinesulfonylureas. However,this reference does not disclose the instant compound or the blackgrassutility therein.

SUMMARY OF THE INVENTION

The present invention is directed to a compound of Formula I ##STR4##and its agriculturally suitable salts, hydrates and complexes with C₁-C₄ alcohols such as methanol, ethanol, pyranol, isopropanol and thedifferent butyl alcohols.

The compound of the invention is highly active as a preemergent and/orpostemergent herbicide for the control of blackgrass. It is especiallyuseful for the selective control of blackgrass in cereal crops.

This invention also comprises a novel compound of Formula II which isuseful as an intermediate to the compound of Formula I

DETAILED DESCRIPTION OF THE INVENTION Synthesis

The compound of Formula I can be synthesized by one or more of thegeneral methods described in U.S. Pat. No. 4,774,337 and U.S. Pat. No.4,456,469: ##STR6## where J and A are as defined below. Alternatively,the compounds of Formula I can be synthesized by the reactions shown inEquations 1a and 1b. The reaction of sulfonamide II with the phenylester of the appropriate carbamic acid IIIa in the presence of variousbases such as a tertiary amine base, 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU) for example, is shown in Equation 1a.

The reaction of sulfonamide II with the phenyl ester of the appropriatecarbamic acid IIIa in the presence of various bases such as a tertiaryamine base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) for example, isshown in Equation 1a. ##STR7##

The reaction shown in Equation 1a is best carried out at 25° C. in asolvent such as, but not limited to, dioxane, tetrahydrofuran,dimethylformamide, dimethylacetamide or acetonitrile for 0.5-24 hoursunder an inert atmosphere as described in European Patent ApplicationNo. 70,804 (published Jan. 26, 1983). The addition of a base isadvantageous. Bases especially suitable are1,5-diazabicyclo[4,3,0]non-5-ene (DBN),1,5-diazabicyclo[5,4,0]undec-5-ene (DBU) or triethylamine. The desiredproduct of Formula I can be conveniently isolated by acidifying thereaction solution with aqueous hydrochloric acid. Alternatively, theaqueous layer can be extracted with a solvent such as methylene chlorideor ethyl acetate. Drying and evaporation of the solvent affords thedesired product. The phenyl carbamate can be synthesized by treatment ofthe corresponding heterocyclic amine of Formula A--NH₂ with diphenylcarbonate or phenyl chloroformate in the presence of a base such assodium hydride, pyridine, or potassium carbonate with a catalytic amountof a catalyst, such as, 4-dimethylaminopyridine. The mixture is stirredat temperatures between 25° C. and 65° C. in a suitable solvent such astetrahydrofuran for 12-36 hours.

The compound of Formula I can also be synthesized by the reaction of theappropriate arylsulfonylcarbamates of Formula IIIc with the heterocyclicamine IIId as shown in Equation 1b. This reaction can be carried out inthe presence of various bases as described in Equation 1a, or by simplyrefluxing in an appropriately high boiling solvent such as dioxane. Thearylsulfonylcarbamates can be synthesized by the reaction of sulfonamideII with phenyl or alkyl carbonates IIIb (or the correspondingchloroformates) in the presence of a variety of bases. ##STR8## wherein

R₂ is phenyl or C₁ -C₄ alkyl; and

J and A are as previously defined.

The required sulfonamide of Formula II can be synthesized by either oneof the methods shown below in Equations 2 and 3.

Equation 2 depicts the reaction of the sulfonyl chloride of Formula IVwith ammonia to give sulfonamide of Formula II. ##STR9## wherein

J is as previously defined.

The amination of Equation 2 is conveniently effected by adding at leasttwo molar equivalents of either anhydrous ammonia or concentratedammonium hydroxide to a solution of the sulfonyl chloride IV in asuitable solvent such as diethyl ether, tetrahydrofuran or methylenechloride at temperatures between -30° C. and 25° C. The desiredsulfonamide of Formula II is isolated either by filtration, in whichcase the by-product ammonium chloride is removed by washing with water,or extraction into a suitable organic solvent such as methylene chlorideor ethyl acetate. Drying and evaporation of the solvent then affords theproduct II which is usually sufficiently pure to be carried directly onto the next step.

The sulfonamide of Formula II can also be prepared as shown in Equation3 by treatment of the corresponding N-t-butylsulfonamide VI with anexcess of an acid such as trifluoroacetic (TFA), polyphosphoric (PPA),or p-toluenesulfonic acid (p-TSA). ##STR10## wherein

J is as previously defined.

The reaction of Equation 3 is conveniently carried out by stirring asolution of the compound of Formula VI in excess trifluoroacetic acid(approximately 0.3M) at about 25° C. for 1-72 hours. The desiredsulfonamide of Formula II is then isolated by removal of the volatilesin vacuo and crystallization from a suitable solvent such as diethylether, 1-chlorobutane, or ethyl acetate. Alternatively, theN-t-butylsulfonamide of Formula VI can be treated with a catalyticamount of p-toluenesulfonic acid monohydrate in a solvent such astoluene or xylenes at reflux temperature for 1-6 hours. The desiredproduct is then isolated in a manner analogous to the one describedabove. For use of polyphosphoric acid in the deprotection ofN-t-butylsulfonamides, see J. G. Lombardino, J. Org. Chem., 1971, 36,1843-1845; for use of trifluoroacetic acid, see J. D. Catt and W. L.Matier, J. Org. Chem., 1974, 39, 566-568.

The sulfonamide of Formula VI can be prepared by the reaction of thesulfonyl chloride of Formula IV with excess t-butyl amine as shown inEquation 4. ##STR11## wherein

J is as previously defined.

The sulfonyl chloride of Formula IV can be prepared according to theprocedures described in U.S. Pat. No. 4,456,469. Alternatively, theprocedures of U.S. Pat. No. 4,741,764 may be utilized which describedthe conversion of mercapto or arylmethylthio compounds to sulfonylchlorides via treatment with hypochlorite solution.

The sulfides of Formula V can be prepared by the reaction of a halopyridine compound of Formula VII with an appropriate mercaptan in thepresence of a base as described in U.S. Pat. No. 4,456,469 and shown inEquation 5. ##STR12## wherein

X' is F, Cl, or Br; and

R' is C₁ -C₄ alkyl or benzyl.

A method to prepare the sulfonamide of Formula VIIIe is shown inEquation 6. The trifluoromethyl ketone intermediate VIIIa is preparedaccording to the procedures of Lang et al., Helv. Chim. Acta. 1988, 71,596-601. In a modification of this procedure, VIIIa is then treated withethyl malonate monoamide (or ethyl carbamoylacetate) in the presence ofsodium methoxide to afford the trifluoromethyl pyridinone methyl esterVIIIb. Heating VIIIb with phosphorous oxybromide or oxalylbromide/dimethylformamide (DMF) in methylene chloride results in thebromopyridine VIIIc. Conversion to the benzyl sulfide VIIId and thesulfonamide VIIIe is carried out as previously described. ##STR13##

Agriculturally suitable salts of the compound of Formula I are alsouseful herbicides and can be prepared in a number of ways known to theart. For example, metal salts can be made by contacting the compound ofFormula I with a solution of an alkali or alkaline earth metal salthaving a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonateor hydroxide). Quaternary amine salts can be made by similar techniques.

Salts of the compound of Formula I can also be prepared by exchange ofone cation for another. For example, cationic exchange can be effectedby direct contact of a solution of a salt of a compound of Formula I(e.g., alkali or quaternary amine salt) with a solution containing thecation to be exchanged. This method is most effective when the desiredsalt containing the exchanged cation is insoluble in the solution andcan be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged for that of the original salt and the desiredproduct is eluted from the column. This method is particularly usefulwhen the desired salt is watersoluble, e.g., a potassium, sodium orcalcium salt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The preparation of the compounds of this invention is furtherillustrated by the following specific examples. Temperatures arereported in degrees Celsius; abbreviations for nuclear magneticresonance (NMR) are: S=singlet, d=doublet, t-triplet, m=multiplet, andpeak positions are reported as parts per million downfield from internaltetramethylsilane. Infrared (IR) peak positions are given in reciprocalcentimeters (cm⁻¹).

EXAMPLE 1 Preparation of methyl1,2-dihydro-2-oxo-6-(trifluoromethyl)-3-pyridinecarboxylate (VIIIb)

To a stirred solution of 2.0 g (0.0102 mol) of4-butoxy-1,1,1-trifluoro-3-buten-2-one (VIIIa) and 1.3 g (0.0102 mol) ofethyl malonate monoamide in 10 mL methyl alcohol was added 2.2 mL(0.0102 mol) of a 25% solution of sodium methoxide in methanol. Thesolution turned into a thick yellow suspension which was refluxedovernight. The suspension was cooled to room temperature, poured intowater, acidified with one normal hydrochloric acid and extracted withmethylene chloride. The combined organic layers were washed with brine,dried over magnesium sulfate and evaporated to afford 1.7 g (74%) of ayellow solid. m.p. 63°-64° C.; ¹ H NMR (CDCl₃) δ4.0 (3H, s), 7.33 (1H,d, J=8 Hz), 8.4 (1H, d, J=8 Hz); IR (mineral oil) 3080, 1675 (br), 1605,1450, 1375 cm⁻¹.

EXAMPLE 2a Preparation of methyl2-bromo-6-(trifluoromethyl)-3-pyridinecarboxylate (VIIIc)

A suspension of 22.0 g (0.100 mol) of the product from Example 1 and28.7 g (0.100 mol) of phosphorous oxybromide was heated at 75°-120° C.over 45 minutes utilizing an oil bath as the heat source. The reactionwas also connected to a water scrubber to trap the gas by-products. Themixture was then cooled to room temperature, diluted with water andextracted with methylene chloride. The combined organic layers werewashed with saturated sodium bicarbonate solution, washed with brine,dried over magnesium sulfate and evaporated to an oil which was purifiedby flesh chromatography utilizing 20% ethyl acetate/petroleum ether asthe eluent to afford 3.8 g (13.3%) of an oil. ¹ H NMR (CDCl₃) δ4.0 (3H,s), 7.72 (1H, d, J=8 Hz), 8.2 (1H, d, J=8 Hz); IR (neat) 1740, 1590,1455, 1335, 1275, 1140, 1100, 1050 cm⁻¹.

EXAMPLE 2b Preparation of methyl2-bromo-6-(trifluoromethyl)-3-pyridinecarboxylate (VIIIc)

To a stirred solution of 2.0 g (0.0091 mol) of the product from Example1 in 25 mL methylene chloride under nitrogen was added 0.92 mL (0.0118mol) of dimethylformamide followed by 1.57 mL (0.011 mol) of oxyalylbromide which resulted in an exotherm to 35° C. and gas evolution beforeall the oxalyl bromide was added. The reaction was cooled to roomtemperature and the remaining oxalyl bromide was added. The solution wasstirred for 1 h at room temperature during which time an orange-yellowsuspension appeared. The reaction was refluxed 3 h, cooled to roomtemperature and stirred overnight. Another 0.79 mL (0.0055 mol) ofoxalyl bromide and 0.46 mL (0.006 mol) of dimethylformamide were addedand refluxed 6 h and then refluxed overnight. Another 0.79 mL (0.0055mol) of oxalyl bromide was added and refluxed 5 h. The reaction waspoured into approximately 50 mL water and to this was added about 150 mLether. The organic layer was separated, washed with brine, dried overmagnesium sulfate and evaporated to an oil which was purified by flashchromatography using 20% ethyl acetate/hexanes as the eluent whichafforded 1.53 g (˜55%) of an oil whose NMR was similar to Example 2a,with the exception of approximately 10% contamination ofdimethyloxalate.

EXAMPLE 3a Preparation of methyl2-[(phenylmethyl)thio]-6-(trifluoromethyl)-3-pyridinecarboxylate (VIIId)

To a stirred suspension of 0.28 g (0.008 mol) of 60% sodium hydride (inmineral oil, then washed with hexanes) in 7 mL dry dimethylformamideunder nitrogen at 0° C. was added 0.8 mL (0.0067 mol) of benzylmercaptan while maintaining the temperature below 10° C. The suspensionwas warmed to room temperature and stirred another 45 minutes beforecooling back to 0° C. A solution of 2.0 g (0.0067 mol) of the productfrom Example 2a or 2b in 5 mL dry dimethylformamide was added dropwiseand stirred 30 minutes at 0° C. The reaction was poured into ice waterand extracted with ether. The combined organic layers were washed withbrine, dried over magnesium sulfate and evaporated to afford 2.3 g(100%). ¹ H NMR (CDCl₃) δ, 3.94 (3H, s), 4.43 (2H, s), 7.2-7.6 (6H, m),8.38 (1H, d, J=8Hz).

EXAMPLE 3b Preparation of methyl2-[(phenylmethyl)thio]-6-(trifluoromethyl)-3-pyridinecarboxylate (VIIId)

To a stirred suspension of 6.55 g (0.0584 mol) of potassium-t-butoxidein 60 mL dry dimethylformamide under nitrogen at 0° C. was added 6.84 mL(0.0584 mol) of benzyl mercaptan in 20 mL dimethylformamide whilemaintaining the temperature below 15° C. A solution of 15.83 g (0.053mol) of the product from Example 2a or 2b in 20 mL dry dimethylformamidewas added dropwise maintaining the temperature at 0° C. and then stirredanother 30 minutes at 0° C. The reaction was poured into ice water andextracted with ether. The combined organic layers were washed withwater, brine, dried over magnesium sulfate and evaporated to afford17.84 g (100%). ¹ H NMR is similar to Example 3. IR (neat) 1725, 1675,1575, 1135, 850 cm⁻¹.

EXAMPLE 4 Preparation of methyl2-[[(1,1-dimethylethyl)amino]-sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate(VIIIe)

To a stirred mixture of 2.3 g (0.007 mol) of the product from Example 3aor 3b in 75 mL methylene chloride and 35 mL water cooled to 0° C. wasadded 2.1 mL (0.025 mol) concentrated hydrochloric acid followed by thedropwise addition of 36 mL (0.0245 mol) of a 5% sodium hypochloritesolution such that the temperature was maintained below 10° C. After themixture was stirred another 15 minutes at 0° C., the reaction was pouredinto water and extracted with methylene chloride. The combined organiclayers were washed with brine, dried over magnesium sulfate andfiltered. The filtrate was stirred and cooled to -70° C. under nitrogen,and 2.6 g (0.035 mol) of t-butyl amine was added dropwise. The mixturewas warmed to -30° C., poured into water and extracted with methylenechloride. The combined organic layers were washed with brine, dried overmagnesium sulfate and evaporated. Purification by flash chromatographyusing 20% ethyl acetate/petroleum ether as the eluent afforded 1.07 g(45%) of a solid. m.p. 76°-83° C.; ¹ H NMR (CDCl₃) δ1.25 (9H, s), 4.0(3H, s), 5.35 (NH), 7.9 (1H, m), 8.2 (1H, m); IR (mineral oil) 3320,1745, 1335, 1140 cm⁻¹.

EXAMPLE 5 Preparation of methyl2-(aminosulfonyl)-6-(trifluoromethyl)-3-pyridinecarboxylate (II)

A solution of 0.95 g (2.79 mmol) of the product from Example 4 wasstirred in 40 mL trifluoroacetic acid at room temperature overnight. Thesolution was evaporated to an oil which was triturated with ether toafford 0.46 g (58%) of a solid. m.p. 187°-188° C. ¹ H NMR (CDCl₃) δ4.05(3H, s), 5.5 (NH₂), 7.95 (1H, d, J=8 Hz), 8.35 (1H, d, J=8 Hz); IR(mineral oil) 3390, 3280, 1725, 1340, 1140 cm⁻¹.

EXAMPLE 6 Preparation of methyl2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate(I)

To a stirred solution of 0.05 g (0.176 mmol) of the product from Example5 and 0.06 g (0.211 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate in 0.5 mL acetonitrile was added dropwise 0.028 g (0.185 mmol)of 1,8-diazabicyclo[5.4.0]undec-7-ene and was stirred 15 minutes. Thesolution was diluted with water, acidified with 1 normal hydrochloricacid and extracted with methylene chloride. The combined organic layerswere washed with brine, dried over magnesium sulfate and evaporated toan oil which was triturated with ether to afford 0.03 g (54%) of asolid. m.p. 130°-137° C. ¹ H NMR (CDCl₃) δ3.96 (6H, s), 4.05 (3H, s),5.82 (1H, s), 7.3 (NH), 7.93 (1H, d, J=approximately 8 Hz), 8.4 (1H, d,J=approximately 8 Hz), 13.1 (NH); IR (mineral oil) 3180, 1745, 1715,1370, 1140 cm⁻¹.

EXAMPLE 7 Preparation of the sodium salt of methyl2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate(I)

To a stirred solution of 50.0 g (0.176 mol) methyl2-(aminosulfonyl)-6-(trifluoromethyl)-3-pyridine-carboxylate and 55.0 g(0.200 mol) phenyl 4,6-dimethoxypyrimidine-2-yl carbamic acid ester in75 mL dimethylformamide was added 30 mL triethylamine at roomtemperature. After dissolution of the solids, the amber solution wasdiluted with 150 mL methanol. To this solution 40 g (0.185 mol) of 25%sodium methoxide solution was slowly added at room temperature. After 10g of the 25% sodium methoxide solution was added, the solution wasseeded with 1.0 g of previously prepared title compound. The resultingprecipitate was cooled to 10° C. and stirred for 30 minutes. The solidprecipitate was filtered and washed with cold methanol (2×50 mL) toafford 75.7 g of a solid, m.p. 176°-177° C. dec. The solid contained3.0% water by Karl Fisher titration and 89.2% of the title compoundwhich was assayed by HPLC. The yield corrected for methyl2-(aminosulfonyl)-6-(trifluoro-methyl)-3-pyridinecarboxylate and theadded seed was 81.4%.

EXAMPLE 8 Preparation of the sodium salt of methyl2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate(I)

To a solution of 9.5 g (0.021 mol) methyl2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylatedissolved in 40 mL methanol was added 5.0 mL (0.023 mol) of 25% sodiummethoxide in methanol. The resulting slurry was stirred at roomtemperature for 40 min. and then filtered to afford 8.3 g of the sodiumsalt, m.p. 172°-173° C. dec. The water content was 5.9% by Karl Fishertitration.

By applying the procedures of U.S. Pat. No. 4,774,337 or Examples 1through 8 and Equations 1 through 6, the compound of Formula I(Compound 1) can be prepared by one skilled in the art.

                  COMPOUND TABLE                                                  ______________________________________                                         ##STR14##                Compound 1                                          ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 0% to 99.9% solid or liquid inertdiluent(s). More specifically, they will contain these ingredients inthe following approximate proportions:

    ______________________________________                                                    Weight Percent*                                                               Active                                                                        Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspension,                                                                              3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  1-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  Filled Film   0.1-90    10-90     0-10                                        ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equal       100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1963, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, Jun. 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed control as a Science", John Wiley and Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE A High Strength Concentrate

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            99%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 trimethylnonyl polyethylene                                                                             1%                                                  glycol ether                                                                  ______________________________________                                    

The surfactant is sprayed upon the active ingredient in a blender andthe mixture sifted through a U.S.S. No. 40 sieve (0.42 mm openings)prior to packaging. The concentrate may be formulated further forpractical use.

EXAMPLE B Wettable Powder

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            65%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 dodecylphenol polyethylene                                                                             2%                                                   glycol ether                                                                  sodium ligninsulfonate   4%                                                   sodium silicoaluminate   6%                                                   montmorillonite (calcined)                                                                             23%                                                  ______________________________________                                    

The ingredients are thoroughly blended. The liquid surfactant is addedby spraying upon the solid ingredients in the blender. After grinding ina hammer mill to produce particles essentially all below 100 microns,the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3mm opening) and packaged.

EXAMPLE C Aqueous Suspension

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                              50.0%                                              amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 polyacrylic acid thickener 0.3%                                               dodecylphenol polyethylene 0.5%                                               glycol ether                                                                  disodium phosphate         1%                                                 monosodium phosphate       0.5%                                               polyvinyl alcohol          1.0%                                               water                      46.7%                                              ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE D Oil Suspension

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            35%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 blend of polyalcohol carboxylic esters                                                                  6%                                                  and oil soluble petroleum sulfonates                                          xylene                   59%                                                  ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 3 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE E Oil Suspension

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            25%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 polyoxyethylene sorbitol  5%                                                  hexaoleate                                                                    highly aliphatic hydrocarbon oil                                                                       70%                                                  ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE F Aqueous Suspension

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                              25%                                                amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 hydrated attapulgite       3%                                                 crude calcium ligninsulfonate                                                                            10%                                                sodium dihydrogen phosphate                                                                              0.5%                                               water                      61.5%                                              ______________________________________                                    

The ingredients are ground together in a ball or roller mill until thesolid particles have been reduced to diameters under 10 microns.

EXAMPLE G Wettable Powder

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                              40.0%                                              amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 dioctyl sodium sulfosuccinate                                                                            1.5%                                               sodium ligninsulfonate     3%                                                 low viscosity methyl cellulose                                                                           1.5%                                               attapulgite                54%                                                ______________________________________                                    

The ingredients are thoroughly blended, passed through an air mill, toproduce an average particle size under 15 microns, reblended, and siftedthrough a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

All compounds of the invention may be formulated in the same manner.

EXAMPLE H Granule

    ______________________________________                                        wettable powder  15%                                                          gypsum           69%                                                          potassium sulfate                                                                              16%                                                          ______________________________________                                    

The ingredients are blended in a rotating mixer and water sprayed on toaccomplish granulation. When most of the material has reached thedesired range of 1.0 to 0.42 mm (U.S.S. No. 18 to 40 sieves), thegranules are removed, dried, and screened. Oversized material is crushedto produce additional material in the desired range. These granulescontain % active ingredient.

EXAMPLE I Wettable Powder

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            50%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 sodium alkylnaphthalenesulfonate                                                                        2%                                                  low viscosity methyl cellulose                                                                          2%                                                  diatomaceous earth       46%                                                  ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air milledto produce particles or active ingredient essentially all below 10microns in diameter. The product is reblended before packaging.

EXAMPLE J Extrude Pellet

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            25%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 anhydrous sodium sulfate 10%                                                  crude calcium ligninsulfonate                                                                           5%                                                  sodium alkylnaphthalenesulfonate                                                                        1%                                                  calcium/magnesium bentonite                                                                            59%                                                  ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinder about 3 mm diameter whichare cut to produce pellets about 3 mm long. These may be used directlyafter drying, or the dried pellets may be crushed to pass a U.S.S. No.20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve(0.42 mm openings) may be packaged for use and the fines recycled.

EXAMPLE K Wettable Powder

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            80%                                                  amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 sodium alkylnaphthalenesulfonate                                                                        2%                                                  sodium ligninsulfonate    2%                                                  synthetic amorphous silica                                                                              3%                                                  kaolinite                13%                                                  ______________________________________                                    

The ingredients are blended and then ground in a hammermill to produceparticles with an average particle size less than 25 microns indiameter. The material is reblended and sifted through a U.S.S. No. 50sieve (0.3 mm opening) before being packaged.

EXAMPLE L High Strength Concentrate

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                                            98.5%                                                amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 silica aerogel           0.5%                                                 synthetic amorphous fine silica                                                                        1.0%                                                 ______________________________________                                    

The ingredients are blended and ground in a hammermill to produce a highstrength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3mm openings). This material may then be formulated in a variety of ways.

EXAMPLE M Solution

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                   amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 sodium salt               5%                                                  water                    95%                                                  ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE N Solution

    ______________________________________                                        Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                   amino]carbonyl]amino]sulfonyl]-6-(trifluoro-                                  methyl)-3-pyridinecarboxylate                                                 sodium salt              50%                                                  aqueous polyvinyl alcohol solution                                                                     49%                                                  sodium dodecylbenzene sulfonate                                                                         1%                                                  ______________________________________                                    

The dry ingredients are ground together and then mixed into thepolyvinyl alcohol solution. The blend is cast as a film of 10-40 mL on aflat surface and then dried to remove the excess water.

UTILITY

Test results indicate that the compound of the present invention is ahighly active preemergent and/or postemergent herbicide or plant growthregulant. The compound has utility for pre- and/or postemergencebroadspectrum grass and broadleaf control in cereal crops. The compoundis particularly useful for the control of blackgrass (Alopecurusmyosuroides) in cereal crops such as wheat (Triticum aestivum), barley(Hordeum vulgare), cats (Avena sativa), rye (Secale cereale) andtriticale (Triticum×Secale).

An effective amount of the compound of this invention is determined by anumber of factors. These factors include: formulation selected, methodof application, amount of vegetation present, growing conditions, etc.In general terms, an effective amount of the compound of the inventionis applied at rates of from 0.001 to 20 kg/ha, with a preferred range offrom 0.002 to 0.25 kg/ha. The compound of this invention may be usedalone or in combination with other commercial herbicides, insecticides,or fungicides. The following list exemplifies some of the herbicidessuitable for use in mixtures. A combination of the compound of thisinvention with one or more of the following herbicides may beparticularly useful for weed control in cereal crops.

    ______________________________________                                        Common Name   Chemical Name                                                   ______________________________________                                        amidosulfuron N-[[[[(4,6-dimethoxy-2-pyrimidinyl)-                                          amino]carbonyl]amino]sulfonyl]-N-                                             methylmethanesulfonamide                                        barban        4-chloro-2-butynyl 3-chlorocarbamate                            bensulfuron   2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)-                           methyl        amino]carbonyl]amino]sulfonyl]-                                               methyl]benzoic acid, methyl ester                               bentazon      3-(1-methylethyl)-(1H)-2,1,3-benzo-                                           thiadiazin-4(3H)-one, 2,2-dioxide                               benzoylprop   N-benzoyl-N-(3,4-dichlorophenyl)-DL-                                          alanine                                                         bifenox       methyl 5-(2,4-dichlorophenoxy)-2-                                             nitrobenzoate                                                   bromoxynil    3,5-dibromo-4-hydroxybenzonitrile                               butachlor     N-(butoxymethyl)-2-chloro-N-(2,6-                                             diethylphenyl)acetamide                                         chlorpropham  1-methylethyl 3-chlorophenylcarbamate                           chlorsulfuron 2-chloro-N-[[(4-methoxy-6-methyl-                                             1,3,5-triazin-2-yl)amino]-                                                    carbonyl]benzenesulfonamide                                     chlortoluron  N'-(3-chloro-4-methylphenyl)-N,N-                                             dimethylurea                                                    cinmethylin   exo-1-methyl-4-(1-methylethyl)-2-[(2-                                         methylphenyl)methoxy]-7-oxabicyclo-                                           [2.2.1]heptane                                                  DCPA          dimethyl 2,3,5,6-tetrachloro-1,4-                                             benzenedicarboxylate                                            diallate      S-(2,3-dichloro-2-propenyl)bis(1-                                             methylethyl)carbamothioate                                      dicamba       3,6-dichloro-2-methoxybenzoic acid                              dichlobenil   2,6-dichlorobenzonitrile                                        dichlorprop   (±)-2-(2,4-dichlorophenoxy)propanoic                                       acid                                                            dichlofop     (±)-2-[4-(2,4-dichlorophenoxy)-                                            phenoxy]propanoic acid                                          difenzoquat   1,2-dimethyl-3,5-diphenyl-1H-                                                 pyrazolium                                                      diflufenican  2',4'-difluoro-2-(α,α,α-trifluoro-m-                        tolyloxy)nicotinanilide                                         DNOC          2-methyl-4,6-dinitrophenol                                      fenoxaprop-ethyl                                                                            ethyl (±)-2-[4-[(6-(chloro-2-benz-                                         oxazolyl)oxy]phenoxy]propanoate                                 fenoxaprop-ethyl                                                                            with crop safener                                               flamprop      N-benzoyl-N-(3-chloro-4-fluoro-                                               phenyl)-DL-alanine                                              fluazifop     (±)-2-[4-[[5-(trifluoromethyl)-2-                                          pyridinyl]oxy]phenoxy]propanoic                                               acid                                                            fluazifop-P   (R)-2-[4-[[5-(trifluoromethyl)-2-                                             pyridinyl]oxy]phenoxy]propanoic                                               acid                                                            fluchloralin  N-(2-chloroethyl)-2,6-dinitro-N-                                              propyl-4-(trifluoromethyl)-                                                   benzenamine                                                     fluorochloridine                                                                            3-chloro-4-(chloromethyl)-1-[3-(tri-                                          fluoromethyl)phenyl]-2-                                                       pyrrolidinone                                                   fluroxypyr    4-amino-3,5-dichloro-6-fluoro-2-                                              pyridyloxyacetic acid                                           imazamethabenz                                                                              6-(4-isopropyl-4-methyl-5-oxo-2-                                              imidazolin-2-yl)- .sub.-- m-toluic acid,                                      methyl ester and 6-(4-isopropyl-4-                                            methyl-5-oxo-2-imidazolin-2-yl)- -p-                                          toluic acid, methyl ester                                       ioxynil       4-hydroxy-3,5-diiodobenzonitrile                                isoproturon   N-(4-isopropylphenyl)-N',N'-                                                  dimethylurea                                                    linuron       N'-(3,4-dichlorophenyl)-N-methoxy-N-                                          methylurea                                                      MCPA          (4-chloro-2-methylphenoxy)acetic acid                           MCPB          4-(4-chloro-2-methylphenoxy)butanoic                                          acid                                                            mecoprop      (±)-2-(4-chloro-2-methylphenoxy)-                                          propanoic acid                                                  mefluidide    N-[2,4-dimethyl-5-[[(trifluoro-                                               methyl)sulfonyl]amino]phenyl]-                                                acetamide                                                       methabenz-    1,3-dimethyl-3-(2-benzothiazolyl)-                              thiazuron     urea                                                            methoxuron    N'-(3-chloro-4-methoxyphenyl)-N,N-                                            dimethylurea                                                    metribuzin    4-amino-6-(1,1-dimethylethyl)-3-                                              (methylthio)-1,2,4-triazin-5(4H)-                                             one                                                             metsulfuron   2-[[[[(4-methoxy-6-methyl-1,3,5-                                methyl        triazin-2-yl)amino]carbonyl]amino]-                                           sulfonyl]benzoic acid, methyl ester                             monuron       N'(4-chlorophonyl)-N,N-dimethylurea                             neburon       1-butyl-3-(3,4-dichlorophenyl)-1-                                             methyl urea                                                     picloram      4-amino-3,5,6-trichloro-2-pyridine-                                           carboxylic acid                                                 PPG-1013      5-[2-chloro-4-(trifluoromethyl)-                                              phenoxy]-2-nitroacetophenone oxime-                                           O-acetic acid, methyl ester                                     propanil      N-(3,4-dichlorophenyl)propanamide                               sulfometuron  2-[[[[(4,6-dimethyl-2-pyrimidinyl)-                             methyl        amino]carbonyl]amino]sulfonyl]-                                               benzoic acid, methyl ester                                      terbuthylazine                                                                              2-(tert-butylamino)-4-chloro-6-                                               (ethylamino)- .sub.- s-triazine                                 terbutryn     N-(1,1-dimethylethyl)-N'-ethyl-6-                                             (methylthio)-1,3,5-triazine-2,4-                                              dismine                                                         thifensulfuron                                                                              [[[[(4-methoxy-6-methyl-1,3,5-                                  methyl        triazin-2-yl)amino]carbonyl]amino]-                                           sulfonyl]-2-thiophenecarboxylic                                               acid, methyl ester                                              triallate     S-(2,3,3-trichloro-2-propenyl) 3-                                             bis(1-methylethyl)carbamothioate                                tribenuron methyl                                                                           2-[[[[N-(4-methoxy-6-methyl-1,3,5-                                            triazine-2-yl)-N-methylamino]-                                                carbonyl]amino]sulfonyl]benzoic                                               acid, methyl ester                                              trifluralin   2,6-dinitro-N,N-dipropyl-4-(tri-                                              fluoromethyl)benzenamine                                        2,4-D         (2,4-dichlorophenoxy)acetic acid                                2,4-DB        4-(2,4-dichlorophenoxy)butanoic acid                            ______________________________________                                    

The selective herbicidal properties of the subject compound that make ituseful as a cereal herbicide was discovered in a number of greenhouseand field tests. The outstanding control of blackgrass (Alopecurusmyosuroides) by the invention compound is particularly demonstrated inresults of three field tests represented by Tables D, E and F. Testdescriptions and results follow.

TEST A

Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloacrus-galli), cheatgrass (Bromus secalinus), cocklebur (Xanthiumpensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass(Digitaria spp.), giant foxtail (Setaria faberi), morningglory (Ipomoeaspp.), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycinemax), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti),wheat (Triticum aestivum), wild oat (Avena fatua) and purple nutsedge(Cyperus rotundus) tubers were planted and treated preemergence withtest chemicals dissolved in a non-phytotoxic solvent. At the same time,these crop and weed species were also treated with postemergenceapplications of test chemicals. Plants ranged in height from two toeighteen cm (two to three leaf stage) for postemergence treatments.Treated plants and controls were maintained in a greenhouse forapproximately sixteen days, after which all species were compared tocontrols and visually evaluated. Plant response ratings, summarized inTable A, are based on a scale of 0 to 10 where 0 is no effect and 10 iscomplete control. A dash (-) response means no test result.

                  TABLE A                                                         ______________________________________                                                         COMPOUND 1                                                   Rate (g/ha)        50      10                                                 ______________________________________                                        POSTEMERGENCE                                                                 Barley             6       2                                                  Barnyardgrass      9       9                                                  Cheatgrass         8       7                                                  Cocklebur          10      10                                                 Corn               9       7                                                  Cotton             9       9                                                  Crabgrass          7       7                                                  Giant foxtail      7       4                                                  Morningglory       3       5                                                  Nutsedge           --      10                                                 Rice               9       9                                                  Sorghum            7       2                                                  Soybean            9       9                                                  Sugar beet         9       9                                                  Velvetleaf         9       8                                                  Wheat              1       0                                                  Wild Oat           3       0                                                  ______________________________________                                        POSTEMERGENCE                                                                 Barley             7       4                                                  Barnyardgrass      9       5                                                  Cheatgrass         7       2                                                  Cocklebur          9       --                                                 Corn               9       7                                                  Cotton             8       7                                                  Crabgrass          8       8                                                  Giant foxtail      5       3                                                  Morningglory       9       8                                                  Nutsedge           10      9                                                  Rice               10      9                                                  Sorghum            7       0                                                  Soybean            9       8                                                  Sugar beet         9       9                                                  Velvetleaf         9       7                                                  Wheat              0       0                                                  Wild Oat           3       0                                                  ______________________________________                                    

TEST B

Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloacrus-galli), blackgrass (Alopecurus myosuroides), chickweed (Stellariamedia), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton(Gossypium hirsutum), crabgrass (Digitaria spp.), downy brome (Bromustectorum), giant foxtail (Setaria faberi), green foxtail (Setariaviridis), jimsonweed (Datura stramonium), johnsongrass (Sorghumhalepense), lambsquarters (Chenopodium album), morningglory (Ipomoeaspp.), rape (Brassica napus), rice (Oryza sativa), sicklepod (Cassiaobtusifolia), soybean (Glycine max), sugar beet (Beta vulgaris), teaweed(Sida spinosa), velvetleaf (Abutilon theophrasti), wheat (Triticumaestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted andtreated preemergence with test chemicals dissolved in a non-phytotoxicsolvent. At the same time, these crop and weed species were also treatedwith postemergence applications of test chemicals. Plants ranged inheight from two to eighteen cm (two to three leaf stage) forpostemergence treatments. Treated plants and controls were maintained ina greenhouse for approximately 24 days, after which all species werecompared to control and visually evaluated. Plant response ratings,summarized in Table B, are reported on a 0 to 10 scale where 0 is noeffect and 10 is complete control. A dash (-) response means no testresult.

                  TABLE B                                                         ______________________________________                                                       COMPOUND 1                                                     Rate (g/ha)      62    16         4   1                                       ______________________________________                                        POSTEMERGENCE                                                                 Barley            3     0          0   0                                      Blackgrass       10    10         10   8                                      Chickweed        10    10         10   9                                      Cocklebur        10    10         10  10                                      Corn             10     8          7   7                                      Cotton           10    10         10   8                                      Crabgrass        10     6          5   4                                      Downy brome       9     3          0   0                                      Giant foxtail     6     3          0   0                                      Green foxtail     9     6          4   3                                      Jimsonweed       10    10         10  10                                      Johnsongrass      5     3          0   0                                      Lambsquarters    10    10         10   7                                      Morningglory      8     5          5   2                                      Nutsedge         10    10         10   5                                      Rape             10    10         10  10                                      Rice Dry Seed    10     9          7   5                                      Sicklepod        10    10         10  10                                      Soybean          10    10         10   9                                      Sugar beet       10    10         10  --                                      Teaweed          10    10         10   9                                      Velvetleaf       10    10         10   7                                      Wheat             3     0          0   0                                      Wild buckwheat   10    10         10  10                                      Wild oat          4     0          0   0                                      Barnyardgrass    10    10         10  10                                      ______________________________________                                        PREEMERGENCE                                                                  Barley            6     5          3   0                                      Blackgrass        7     6          5   3                                      Chickweed         8     7          7   5                                      Cocklebur        10     8          7   7                                      Corn              7     6          0   0                                      Cotton            8     8          7   5                                      Crabgrass         9     8          7   6                                      Downy brome       5     3          0   0                                      Giant foxtail     7     5          0   0                                      Green foxtail     9     7          5   0                                      Jimsonweed        9     9          9   9                                      Johnsongrass      8     6          3   0                                      Lambsquarters    --    --         --  --                                      Morningglory      8     6          3   0                                      Nutsedge         10    10          8   6                                      Rape             10    10         10  10                                      Rice Dry Seed    10    10         10   7                                      Sicklepod         9     8          8   3                                      Soybean           8     6          5   3                                      Sugar beet       10    10         10  10                                      Teaweed           8     7          7   6                                      Velvetleaf       10    10          8   7                                      Wheat             3     0          0   0                                      Wild buckwheat   10    10          9   9                                      Wild oat          6     3          0   0                                      Barnyardgrass    10    10          8   4                                      ______________________________________                                    

TEST C

Compounds evaluated in this test were formulated in a non-phytotoxicsolvent and applied to the soil surface before plant seedlings emerged(preemergence application) and to plants that were in the one-to-fourleaf stage (postemergence application). A sandy loam soil was used forthe preemergence test while a mixture of sandy loan soil and greenhousepotting mix in a 60:40 ratio was used for the postemergence test. Testcompounds were applied within approximately one day after planting seedsfor the preemergence test. Plants of these crops and weed species wereadjusted to produce plants of appropriate size for the postemergencetest. All plant species were grown using normal greenhouse practices.Crop and weed species include winter barley (Hordeum vulgare cv.`Igri`), bedstraw (Galium aparine), blackgrass (alopecurusmysosuroides), chickweed (Stellaria media), downy brome (Bromustectorum), field violet (Viola arvensis), green foxtail (Setariaviridis), Persian speedwell (Veronica persica), rape (Brassica napus cv.`Jet Neuf`), ryegrass (Lolium multiflorum), sugar beet (Beta vulgariscv. `US1`), sunflower (Helianthus annuus cv. ` Russian Giant`), springwheat (Triticum aestivum cv. `ERA`), winter wheat (Triticum aestivum cv.`Talent`), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapisarvensis), wild oat (Avena fatua), and wild radish (Raphanusraphanistrum). Blackgrass and wild oat were treated postemergence at twogrowth stages. The first stage (1) was when the plants had two to threeleaves. The second stage (2) was when the plants had approximately fourleaves or in the initial stages of tillering. Treated plants anduntreated controls were maintained in a greenhouse for approximately 21to 28 days, after which all treated plants were compared to untreatedcontrols and visually evaluated. Plant response ratings, summarized inTable C, are based upon a 0 to 10 scale where 0 is no effect and 10 iscomplete control. A dash response (-) means no test result.

                  TABLE C                                                         ______________________________________                                                   COMPOUND 1                                                         Rate (g/ha)  125    64      32   16   8     4                                 ______________________________________                                        POSTEMERGENCE                                                                 Blackgrass (1)                                                                             --     --      --   --   --    --                                Blackgrass (2)                                                                             10     10      10   8    6     5                                 Chickweed    10     8       6    4    2     0                                 Downy brome   2     0       0    0    0     0                                 Field violet  4     2       0    0    0     0                                 Galium (1)   10     7       5    4    2     0                                 Green foxtail                                                                              10     9       8    6    4     3                                 Persn Speedwell                                                                             3     2       0    0    0     0                                 Rape         10     10      10   10   10    10                                Ryegrass      6     5       3    0    0     0                                 Sugar beet   10     8       6    6    5     4                                 Sunflower    10     10      10   10   10    10                                Wheat (Spring)                                                                              2     0       0    0    0     0                                 Wheat (Winter)                                                                              2     0       0    0    0     0                                 Wild buckwheat                                                                             10     10      8    6    4     2                                 Wild mustard 10     10      10   10   10    9                                 Wild oat (1)  0     0       0    0    0     0                                 Wild oat (2)  0     0       0    0    0     0                                 Wild radish  10     10      10   10   10    10                                Winter Barley                                                                               4     2       0    0    0     0                                 ______________________________________                                        PREEMERGENCE                                                                  Blackgrass (1)                                                                             10     8       7    7    3     2                                 Blackgrass (2)                                                                             10     10      8    7    4     3                                 Chickweed    10     10      10   10   9     8                                 Downy brome   7     5       4    2    0     0                                 Field violet 10     10      10   10   9     7                                 Galium (1)   10     10      10   10   9     6                                 Green foxtail                                                                              10     8       7    6    4     2                                 Persn Speedwell                                                                            10     10      10   8    7     6                                 Rape         10     10      10   10   10    9                                 Ryegrass      7     6       5    3    2     0                                 Sugar beet   10     10      10   10   9     8                                 Sunflower    10     10      10   10   8     6                                 Wheat (Spring)                                                                              2     1       0    0    0     0                                 Wheat (Winter)                                                                              2     2       0    0    0     0                                 Wild buckwheat                                                                             10     10      8    7    5     3                                 Wild mustard 10     10      10   10   9     8                                 Wild oat (1)  3     2       0    0    0     0                                 Wild oat (2)  4     2       0    0    0     0                                 Wild radish  10     10      10   10   8     6                                 Winter Barley                                                                               6     4       2    0    0     0                                 ______________________________________                                    

TEST D

A field test was sown with seeds of winter wheat (Triticum aestivum),winter barley (Hordeum vulgare) and blackgrass (Alopecurus myosuroides)and treated postemergence with the test chemicals dissolved in anon-phytotoxic solvent. Thirty-six days after treatment the treatedplants were compared to controls and visually evaluated. Plant responseratings, summarized in Table D, are based on a scale of 0 to 10 where 0is no effect and 10 is complete control.

                  TABLE D                                                         ______________________________________                                        COMPOUND 1 (36 DAT)                                                           Rate (g/ha)                                                                            Winter Wheat                                                                              Winter Barley                                                                              Blackgrass                                  ______________________________________                                        70       1           3            10                                          35       1           2            10                                          18       0           1            10                                           8       0           0            10                                          ______________________________________                                    

TEST E

A field test was sown with seeds of winter wheat (Triticum aestivum) andblackgrass (Alopecurus mysuroides) and treated postemergence with thetest chemicals dissolved in a non-phytotoxic solvent. Forty-nine daysafter treatment the treated plants were compared to controls andvisually evaluated. Plant response ratings, summarized in Table E, arebased on a scale of 0 to 10 where 0 is no effect and 10 is completecontrol.

                  TABLE E                                                         ______________________________________                                        COMPOUND 1 (49 DAT)                                                           Rate (g/ha)   Winter Wheat                                                                              Blackgrass                                          ______________________________________                                        64            0           10                                                  32            0           10                                                  16            0           10                                                   8            0            9                                                  ______________________________________                                    

TEST F

A field test was sown with seeds of winter wheat (Triticum aestivum),winter barley (Hordeum vulgare) and blackgrass (Alopecurus myosuroides)and treated postemergence with the test chemicals dissolved in anon-phytotoxic solvent. Sixty-six days after treatment the treatedplants were compared to controls and visually evaluated. Plant responseratings, summarized in Table F, are based on a scale of 0 to 10 where 0is no effect and 10 is complete control.

                  TABLE F                                                         ______________________________________                                        COMPOUND 1 (66 DAT)                                                           Rate (g/ha)                                                                            Winter Wheat                                                                              Winter Barley                                                                              Blackgrass                                  ______________________________________                                        64       0           5            10                                          32       0           5            9                                           16       0           4            8                                            8       0           3            7                                            4       0           2            4                                           ______________________________________                                    

TEST G

Test plants of blackgrass (Alopecurus myosuroides), `Talent` winterwheat (Triticum aestivum) and `Igri` winter barley (Hordeum vulgare)were grown under greenhouse conditions to the 2 leaf stage. Standard 4"fiber pots filled with a mixture of Matapeake sandy loam soil, Sand, andMetro Mix (approximately 50:10:40 by volume) were used.

Compound 1 and the sodium salt of Compound 1 were dissolved into stocksolutions using a small amount (1 ml) of acetone and water,respectively. Appropriate amounts of each stock were brought up to thenormal spray volume (28 mL) in a solution of deionized water and 0.25%(wt/vol) `X-77` surfactant. Treatments were applied to the test plants.Each formulation was tested at 2, 4, 8 and 16 g ai/ha on blackgrass, andat 8, 16, 32 and 64 g ai/ha on the cereal crops. Each treatment wasreplicated four times.

After treatment the test plants were returned to the greenhouse forperiodic evaluation. At 21 days after treatment, blackgrass control andcereal crop injury were evaluated visually. The visual rating scale usedis from 0 to 100% control, where 0 represents no visual symptomsrelative to an untreated control, and 100% represents complete kill. Arating of 20% or greater on the cereal crops represents an unacceptablelevel of crop injury on this scale.

                  TABLE G                                                         ______________________________________                                        COMOUND 1 AND COMPOUND 1 SODIUM SALT                                          FORMULATED AS TECHNICAL OR IN PVOH FILM                                                        Weed and Crop Species*                                       Formulation  Rate      (% phytotoxicity)                                      Compound 1   (g ai/ha) BKG      WWT    BWI                                    ______________________________________                                        Untreated     0          0**     0      0                                     PVOH Film Check                                                                             0         0        0      0                                     Compound 1    2        60       --     --                                     (95% ai)      4        74       --     --                                                   8        86        0      3                                                  16        90        0     10                                                  32        --       10     23                                                  64        --       25     38                                     Compound 1    2        60       --     --                                     Sodium Salt   4        78       --     --                                     (95% ai)      8        88        0      3                                                  16        93        3     13                                                  32        --        8     23                                                  64        --       23     40                                     Compound 1    2        60       --     --                                     in PVOH       4        75       --     --                                     (approx.      8        85        0      3                                     45% ai)      16        90        0     10                                                  32        --        5     25                                                  64        --       20     38                                     Compound 1    2        58       --     --                                     Sodium Salt   4        79       --     --                                     in PVOH       8        88        0      3                                     (approx.     16        90        0     18                                     45% ai)      32        --        5     23                                                  64        --       13     35                                     ______________________________________                                         PVOH = polyvinyl alcohol                                                      *Weed and crop Species; BKG = blackgrass, WWT = winter wheat `Talent` BWI     = winter baley `Igri`-                                                        **Each number represents the average of four observations                

What is claimed is:
 1. A compound of the formula ##STR15## and itsagriculturally suitable salts, hydrates and complexes with C₁ -C₄alcohols.
 2. The compounds of claim 1 which are agriculturally suitablesalts of the compound of Formula I.
 3. The compounds of claim 1 whereinthe salt is sodium.
 4. An agriculturally suitable composition forcontrolling the growth of undesired vegetation comprising an effectiveamount of the compound of claim 1 and at least one of the following:surfactant, solid or liquid diluent.
 5. An agriculturally suitablecomposition for controlling the growth of undesired vegetationcomprising an effective amount of the compound of claim 2 and at leastone of the following: surfactant, solid or liquid diluent.
 6. Anagriculturally suitable composition for controlling the growth ofundesired vegetation comprising an effective amount of the compound ofclaim 3 and at least one of the following: surfactant, solid or liquiddiluent.
 7. A method for controlling the growth of undesired vegetationwhich comprises adding to the locus to be protected an effective amountof a compound of claim
 1. 8. A method for controlling the growth ofundesired vegetation in cereal crops which comprises adding to the locusto be protected an effective amount of a compound of claim
 1. 9. Amethod for controlling the growth of blackgrass which comprises applyingto the locus to be protected an effective amount of a compound ofclaim
 1. 10. A method for controlling the growth of blackgrass whichcomprises applying to the locus to be protected an effective amount of acompound of claim 3.